The present invention relates to a process of producing ring-opening polymerization products and more particularly it relates to a process of producing a ring-opening polymerization product at a high polymerization activity by subjecting a norbornene derivative containing at least one polar group or aromatic group, a norbornadiene derivative containing at least one of said groups or a cycloolefin to a ring-opening polymerization in the presence of, if desired, an unsaturated polymer, using a catalyst system prepared from an organometallic compound and the reaction product of tungsten oxide or molybdenum oxide and a phosphorus pentahalide or phosphorus oxytrihalide or these compounds and other third components. It has been discovered that a novel and useful ring-opening polymerization product is obtained by polymerizing a norbornene derivative containing at least one cyano group, ester group, acid anhydride group, ether group, imide group, halogen atom or aromatic group, norbornadiene derivatives containing at least one of said groups, a cycloolefin or a mixture of at least one of the aforesaid derivatives using a catalyst system prepared from a tungsten compound or a molybdenum compound and an organometallic compound or these compounds and other third components such as, an organic peroxide, an acetalic compound, and an alcoholic compound as described in the specifications of our U.S. Pat. No. 3,856,758; Japanese Patent Application Laid Open Nos. 77,999/74; 58,200/75; 61,500/75; 71,800/75; 75,300/75; 103,600/75; 110,000/75 and 153,100/75.
Some of the ring-opening polymerization products obtained by the aforesaid processes are superior to polyvinyl chloride resin and polypropylene resin which have now been manufactured on an industrial scale and widely used in various industrial fields in not only the mechanical properties such as impact strength, low-temperature impact strength and tensile strength but also heat resistance and transparency. Furthermore, these polymerization products can be fabricated or molded into various forms by applying to a fabrication or molding method which has widely been employed in the field of thermoplastic resins, such as injection molding, extrusion molding, blow molding, compression molding and can be used for various purposes as containers, films, sheets, pipers and the like. Moreover, the properties of these polymerization products can be improved for fitting desired purposes by blending together with a thermoplastic resin such as a polyvinyl chloride riesin, a polymethyl-methacrylate resin, etc.; said thermoplastic resin also including an impact resistant resin such as an ABS resin and an ACS resin; a heat resistant resin such as a polyacetal resin, a polyamide resin, etc.; and/or a rubber-like material such as a polybutadiene rubber, a chlorinated polyethylene rubber, etc., or further by adding thereto various additives.
Still further, some other ring-opening polymerization products prepared by the aforesaid processes can be used, as is or following the polymer reaction, as ion-exchange resins, adhesives, and flocculants.
Also, it has been proposed to produce a ring-opening polymerization product by polymerizing a cycloolefinic compound such as cyclopentene using a catalyst system comprising tungsten oxide and/or molybdenum oxide and a Lewis acid such as aluminum chloride, titanium tetrachloride, tin tetrachloride, vanadium tetrachloride, etc., or these components and an organometallic compound of a metal belonging to Groups I to IV of the periodic table, in particular an organoaluminum compound as described in the specifications of Japanese Patent Application Laid Open Nos. 17,389/72; 39,388/72; and 39,599/73. The polymerization products obtained by these processes are suitable as rubber-like materials owing to their excellent elastic property.
Furthermore, it has been discovered that the same ring-opening polymerization products of the norbornene derivatives as mentioned above can be obtained by using the catalyst system described in the above-mentioned specifications (Japanese Patent Application No. 18470/74). However, even if a cycloolefin or norbornene derivative is polymerized in the presence of a catalyst system comprising tungsten trioxide and aluminum chloride or these compounds and an organoaluminum compound which is described as having the highest polymerization activity in the above-mentioned specifications, the polymerization activity is yet unsatisfactory.
Since the polar group present in the monomer as used in the present invention is known to inactivate the catalyst system thereby markedly decreasing the catalytic activity, attempts to obtain catalyst systems possessing excellent catalytic activity for the ring-opening polymerization of norbornene derivatives containing a polar group have not succeeded.